Omega-halo-2-alkynal

ABSTRACT

Provided is a method for industrially producing a conjugated Z-alken-yn-yl acetate such as Z-13-hexadecen-11-yn-yl acetate which is a sex pheromone component of a pine processionary moth, and an intermediate for the conjugated Z-alken-yn-yl acetate under mild conditions at a high yield. More specifically, provided is a method for producing a conjugated Z-alken-yn-yl acetate (5) comprising the steps of: reacting an ω-halo-2-alkynal (1) with an alkylidene triphenylphosphorane (3) through a Wittig reaction to obtain a conjugated Z-alken-yn-yl halide (4), and acetoxylating the conjugated Z-alken-yn-yl halide (4) into a conjugated Z-alken-yn-yl acetate (5).

RELATED APPLICATION

This application claims priority from Japanese Patent Application No. 2013-083861, filed Apr. 12, 2013, the disclosure of which is incorporated by reference herein in its entirety.

FIELD AND BACKGROUND OF THE INVENTION

The present invention relates to methods for producing a conjugated Z-alken-yn-yl acetate and an ω-halo-2-alkynal which is an intermediate thereof, particularly to a method for producing Z-13-hexadecen-11-yn-yl acetate which is a sex pheromone component of a pine processionary moth (scientific name: Thaumetopoea pityocampa), which is a forest pest insect in Europe.

A pine processionary moth (scientific name: Thaumetopoea pityocampa) is an insect widely inhabiting European countries such as France, Italy, Spain, Portugal and Greece. It has become a problem as a forest pest insect because of feeding damage to trees such as pine and cedar. In addition, poisonous hair of the larva of this moth is known to cause a serious allergic reaction in humans, livestock, pets and the like. Moreover, in recent years, the habitat of the moth has been expanding northward from the Mediterranean region due to the effect of global warming. There is therefore a demand for the development of a novel control method of the moth.

It has been reported by A. Guerrero et al. in 1981 (A. Guerrero et. al., Tetrahedron Letters, Vol. 22, 2013-2016, 1981) that the sex pheromone component of this pine methodionary moth is Z-13-hexadecen-11-yn-yl acetate having a conjugated Z-alken-yn-yl acetate structure. Development of a control method such as mating disruption or mass trapping using this sex pheromone has therefore been expected.

The methods for producing Z-13-hexadecen-11-yn-yl acetate that have already been reported include: a method reported by F. Camps et al. and making use of an elimination reaction of a secondary tosylate and use of an organolithium compound (Spanish Patent Publication No. 2010719, Spanish Patent Publication No. 8204407, and F. Camps et. al., Chem. Lett., 703, 1981), a method reported by G. Cardillo et al. and using lithium diisopropylamide and a dehydration reaction (G. Cardillo et. al., Gazzetta Chimica Italiana, 112, 231, 1982), a method reported by J. K. Stille et al. and using an acetylene zipper reaction, an organotin compound, and diimide reduction (J. K. Stille et. al., J. Am. Chem. Soc., 1987, 109, 2138), a method reported by M. Gardette et al. and using a reaction between an organocopper lithium reagent and an acetylene compound (M. Gardette et. al., J. Chem. Ecolg., 9, 219, 1983), and a method reported by D. Michelot et al. and using a hydroboration reaction and a coupling reaction in the presence of a palladium catalyst (D. Michelot et. al., J. Chem. Res., 4, 1043, 1982). Thus, in these methods, a special raw material such as an organolithium compound, an organoboron compound, an organotin compound or a diimide compound is used and a step of requiring a low-temperature reaction at −10° C. or less for the production is comprised.

On the other hand, as a method for producing Z-13-hexadecen-11-yn-yl acetate under mild conditions without using a special raw material, there has been reported a production method using a Wittig reaction between 13-tetrahydropyranoxy-2-tridecyn-1-al obtained by protecting an alcohol group at the C13-position with a tetrahydropyranyl group and propylidene triphenylphosphorane (F. Camps et. al., J. Chem. Ecolg., 9, 869, 1983).

SUMMARY OF THE INVENTION

It has been reported in the most of the methods for producing Z-13-hexadecen-11-yn-yl acetate that a special raw material such as an organolithium compound, an organoboron compound, an organotin compound, or a diimide compound is used and a step of requiring a low temperature reaction at −10° C. or less is comprised. Accordingly, the methods have many problems for an industrial mass production to be used in practice from the standpoints of safety, production equipment, production cost and the like. The production method through a Wittig reaction which can be carried out under mild conditions is effective as an industrial production method, but has some problems such as reduction of yield owing to inclusion of more steps including protection and deprotection steps of the terminal co-alcohol group, and a low yield in the Wittig reaction.

With the foregoing in view, the invention has been made. An object of the invention is to overcome the problems of the conventional art and provide a method for industrially producing a conjugated Z-alken-yn-yl acetate such as Z-13-hexadecen-11-yn-yl acetate which is the sex pheromone component of a pine methodionary moth and an intermediate for the conjugated Z-alken-yn-yl acetate, under mild conditions at a high yield.

The present inventors have found that use of an ω-halo-2-alkynal having a halogen group as the terminal co-functional group and represented by formula (1):

-   -   wherein X represents a halogen atom and n stands for an integer         of from 2 to 15,         makes it possible to produce a conjugated Z-alken-yn-yl halide         without conducting protection and deprotection steps and to keep         a good yield even in a subsequent Wittig reaction. They have         also found that the conjugated Z-alken-yn-yl halide can be         converted into a corresponding acetate at a good yield by a         single step and the intended conjugated Z-alken-yn-yl acetate         such as Z-13-hexadecen-11-yn-yl acetate can be produced         efficiently. Such findings have led to the completion of the         invention.

In the present invention, there is provided a method for producing an ω-halo-2-alkynal comprising a step of hydrolyzing an ω-halo-1,1-dialkoxy-2-alkyne represented by formula (2):

-   -   wherein R¹ and R² may be the same or different and each         represents a linear, branched or cyclic C₁₋₁₀ hydrocarbon group,         X represents a halogen atom, and n stands for an integer of from         2 to 15,         in water and an organic solvent in the presence of sulfonic acid         to form a ω-halo-2-alkynal represented by the formula (1).

In the present invention, there is also provided a method for producing a conjugated Z-alken-yn-yl acetate comprising the steps of hydrolyzing an ω-halo-1,1-dialkoxy-2-alkyne represented by formula (2):

-   -   wherein R¹ and R² may be the same or different and each         represents a linear, branched or cyclic C₁₋₁₀ hydrocarbon group,         X represents a halogen atom, and n stands for an integer of from         2 to 15         in water and an organic solvent in the presence of sulfonic acid         to form a ω-halo-2-alkynal represented by the formula (1),         reacting the ω-halo-2-alkynal with an alkylidene         triphenylphosphorane represented by formula (3):         RCH═PPh₃  (3)     -   wherein R represents a linear, branched, or cyclic C₁₋₁₂         hydrocarbon group and Ph represents a phenyl group,         to obtain a conjugated Z-alken-yn-yl halide represented by         formula (4):

and acetoxylating the conjugated Z-alken-yn-yl halide into a conjugated Z-alken-yn-yl acetate represented by formula (5):

In the present invention, there is further provided an ω-halo-2-alkynal represented by formula (1) wherein n stands for an integer of from 2 to 4, 6, 7 and 10 to 15.

According to the invention, a conjugated Z-alken-yn-yl acetate such as Z-13-hexadecen-11-yn-yl acetate which is the sex pheromone component of a pine methodionary moth, can be industrially produced under mild conditions with high efficiency.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention now will be described more fully hereinafter in which embodiments of the invention are provided with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All references cited are incorporated herein by reference in their entirety.

The ω-halo-2-alkynal is represented by the following formula (1) and it is, for example, 13-chloro-2-tridecynal

In the formula (1), X represents a halogen atom such as chlorine, bromine or iodine. Of these, chlorine and bromine atoms are particularly preferred as the halogen atom from the standpoints of a yield and availability of raw materials. In addition, n stands for an integer of from 2 to 15, preferably an integer of from 4 to 10, more preferably an integer of from 6 to 10. Specific examples of (CH₂)_(n) include an alkylene group such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene.

Specific examples of the ω-halo-2-alkynal (1) include an ω-chloro-2-alkynal such as 5-chloro-2-pentynal, 6-chloro-2-hexynal, 7-chloro-2-heptynal, 8-chloro-2-octynal, 9-chloro-2-nonynal, 10-chloro-2-decynal, 11-chloro-2-undecynal, 12-chloro-2-dodecynal and 13-chloro-2-tridecynal, and an ω-bromo-2-alkynal such as 5-bromo-2-pentynal, 6-bromo-2-hexynal, 7-bromo-2-heptynal, 8-bromo-2-octynal, 9-bromo-2-nonynal, 10-bromo-2-decynal, 11-bromo-2-undecynal, 12-bromo-2-dodecynal and 13-bromo-2-tridecynal.

The ω-halo-2-alkynal represented by the formula (1) can be produced by hydrolyzing the dialkylacetal portion of an ω-halo-1,1-dialkoxy-2-alkyne represented by the following formula (2) in water and an organic solvent in the presence of an acid catalyst. For example, 13-chloro-2-tridecynal can be produced by hydrolyzing 13-chloro-1,1-diethoxy-2-tridecyne in the presence of an acid catalyst in water and an organic solvent.

In the formula (2), R¹ and R² are the same or different and each represents a linear, branched or cyclic C₁₋₁₀ hydrocarbon group. Specific examples include a linear hydrocarbon group such as methyl, ethyl, propyl and butyl; a branched hydrocarbon group such as isopropyl, isobutyl, sec-butyl and tert-butyl; and a cyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Preferred are a linear hydrocarbon group such as methyl, ethyl, propyl and butyl, with methyl and ethyl groups being more preferred.

X and n have the same meanings as described above and preferred examples of each of them are also as described above.

Specific examples of the ω-halo-1,1-dialkoxy-2-alkyn (2) include an ω-chloro-1,1-dimethoxy-2-alkyne such as 5-chloro-1,1-dimethoxy-2-pentyne, 6-chloro-1,1-dimethoxy-2-hexyne, 7-chloro-1,1-dimethoxy-2-heptyne, 8-chloro-1,1-dimethoxy-2-octyne, 9-chloro-1,1-dimethoxy-2-nonyne, 10-chloro-1,1-dimethoxy-2-decyne, 11-chloro-1,1-dimethoxy-2-undecyne, 12-chloro-1,1-dimethoxy-2-dodecyne and 13-chloro-1,1-dimethoxy-2-tridecyne; an ω-bromo-1,1-dimethoxy-2-alkyne such as 5-bromo-1,1-dimethoxy-2-pentyne, 6-bromo-1,1-dimethoxy-2-hexyne, 7-bromo-1,1-dimethoxy-2-heptyne, 8-bromo-1,1-dimethoxy-2-octyne, 9-bromo-1,1-dimethoxy-2-nonyne, 10-bromo-1,1-dimethoxy-2-decyne, 11-bromo-1,1-dimethoxy-2-undecyne, 12-bromo-1,1-dimethoxy-2-dodecyne and 13-bromo-1,1-dimethoxy-2-tridecyne; an ω-chloro-1,1-diethoxy-2-alkyne such as 5-chloro-1,1-diethoxy-2-pentyne, 6-chloro-1,1-diethoxy-2-hexyne, 7-chloro-1,1-diethoxy-2-heptyne, 8-chloro-1,1-diethoxy-2-octyne, 9-chloro-1,1-diethoxy-2-nonyne, 10-chloro-1,1-diethoxy-2-decyne, 11-chloro-1,1-diethoxy-2-undecyne, 12-chloro-1,1-diethoxy-2-dodecyne and 13-chloro-1,1-diethoxy-2-tridecyne; and an ω-bromo-1,1-diethoxy-2-alkyne such as 5-bromo-1,1-diethoxy-2-pentyne, 6-bromo-1,1-diethoxy-2-hexyne, 7-bromo-1,1-diethoxy-2-heptyne, 8-bromo-1,1-diethoxy-2-octyne, 9-bromo-1,1-diethoxy-2-nonyne, 10-bromo-1,1-diethoxy-2-decyne, 11-bromo-1,1-diethoxy-2-undecyne, 12-bromo-1,1-diethoxy-2-dodecyne and 13-bromo-1,1-diethoxy-2-tridecyne.

The ω-halo-1,1-dialkoxy-2-alkyne represented by the formula (2) can be produced, for example, by the method described in JP 2-101028A or JP 2005-272409A. More specifically, as described in JP 2-101028A, an ω-halo-1,1-dialkoxy-2-alkyne can be obtained by reacting an ω-halo-1-alkyne with an alkyl magnesium halide and then with an alkyl orthoformate. When the raw material used is an ω-halo-1-alkyne having a long methylene chain which is not easily available, as described in JP 2005-272409A, an ω-halo-1,1-dialkoxy-2-alkyne having a long methylene chain can be obtained by reacting the ω-halo-1-alkyne with an alkyl magnesium halide to protect the terminal alkyne, reacting the resulting product with metal magnesium to form a corresponding Grignard reagent, subjecting the Grignard reagent to a cross-coupling reaction with a 1-bromo-ω-chloroalkane in the presence of a copper halide catalyst, and then reacting the resulting product with an alkyl orthoformate. Alternatively, the ω-halo-1,1-dialkoxy-2-alkyne having a long methylene chain may be produced by isolating and purifying the ω-halo-1-alkyne having a long methylene chain after the above-mentioned cross-coupling reaction, reacting the isolated and purified ω-halo-1-alkyne with an alkyl magnesium halide again, and then reacting the resulting product with an alkyl orthoformate.

The acid catalyst to be used in the hydrolysis reaction for forming an aldehyde is not particularly limited. Specific examples thereof include an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid; a carboxylic acid such as formic acid, acetic acid, oxalic acid, trifluoroacetic acid, difluoroacetic acid, trichloroacetic acid, dichloroacetic acid and monochloroacetic acid; and a sulfonic acid such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid. The acid may be used singly or in combination of two or more acids. Of these examples, a sulfonic acid such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid are particularly preferred from the standpoints of a reaction rate, an amount of impurity formed, and a yield. The acid catalyst is used in an amount of preferably from 0.01 to 0.1 mol per mol of the ω-halo-1,1-dialkoxy-2-alkyne (2). The acid catalyst is used in an amount of particularly preferably from 0.03 to 0.05 mol per mol of the ω-halo-1,1-dialkoxy-2-alkyne (2) from the standpoints of a reaction rate, an amount of impurity formed, and a yield.

In the hydrolysis reaction for forming an aldehyde, water is also used. Water is used in an amount of preferably from 30 to 300 g per mol of the ω-halo-1,1-dialkoxy-2-alkyne (2). Water is used in an amount of particularly preferably from 100 to 250 g per mol of the ω-halo-1,1-dialkoxy-2-alkyne (2) from the standpoints of a reaction rate and a yield per volume of a reactor.

In the hydrolysis reaction for forming an aldehyde, the organic solvent is not particularly limited insofar as it does not adversely affect the reaction. A water-soluble organic solvent is preferred from the standpoint of reactivity. Examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, tetrahydrofuran, acetone, N,N-dimethylformamide and N,N-dimethylacetamide. Tetrahydrofuran is particularly preferred from the standpoint of reactivity. The organic solvent is used in an amount of preferably from 10 to 200 g per mol of the ω-halo-1,1-dialkoxy-2-alkyne (2). The organic solvent is used in an amount of particularly preferably from 30 to 100 g per mol of the ω-halo-1,1-dialkoxy-2-alkyne (2) from the standpoints of a reaction rate and a yield per volume of a reactor.

The temperature of the hydrolysis reaction for forming an aldehyde is preferably from 30 to 120° C. It is particularly preferably from 60 to 85° C. from the standpoints of a reaction rate, an amount of impurity formed, and a yield. An alcohol formed as a by-product in the hydrolysis reaction may be distilled off from a reactor under normal pressure or reduced pressure.

Next, the ω-halo-2-alkynal (1) is reacted with an alkylidene triphenylphosphorane (3) through a Wittig reaction to produce a conjugated Z-alken-yn-yl halide (4). For example, Z-13-hexadecen-11-yn-yl chloride can be produced by reacting 13-chloro-2-tridecynal with propylidene triphenylphosphorane.

X and n have the same meanings as described above and preferred examples of each of them are also as described above. Ph represents a phenyl group.

R represents a linear, branched or cyclic C₁₋₁₂ hydrocarbon group. Specific examples thereof include a linear hydrocarbon group such as methyl, ethyl and propyl; a branched hydrocarbon group such as isopropyl, isobutyl, sec-butyl and tert-butyl; and a cyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Preferred is a linear C₁₋₁₂ hydrocarbon group, with a linear C₁₋₆ hydrocarbon group being more preferred.

Specific examples of the alkylidene triphenylphosphorane (3) include ethylidene triphenylphosphorane, propylidene triphenylphosphorane, butylidene triphenylphosphorane, pentylidene triphenylphosphorane, propylidene triphenylphosphorane, isopropylmethylidene triphenylphosphorane, isobutylmethylidene triphenylphosphorane, sec-butylmethylidene triphenylphosphorane, tert-butylmethylidene triphenylphosphorane, cyclopropylmethylidene triphenylphosphorane, cyclobutylmethylidene triphenylphosphorane and cyclopentylmethylidene triphenylphosphorane.

Specific examples of the conjugated Z-alken-yn-yl halide (4) include a conjugated Z-alken-yn-yl chloride such as Z-7-decen-5-yn-yl chloride, Z-9-dodecen-7-yn-yl chloride, Z-9-undecen-7-yn-yl chloride, Z-10-dodecen-8-yn-yl chloride, Z-11-tridecen-9-yn-yl chloride, Z-12-tetradecen-10-yn-yl chloride, Z-13-pentadecen-11-yn-yl chloride, Z-9-dodecen-7-yn-yl chloride, Z-10-tridecen-8-yn-yl chloride, Z-11-tetradecen-9-yn-yl chloride, Z-12-pentadecen-10-yn-yl chloride, Z-13-hexadecen-11-yn-yl chloride, Z-9-tridecen-7-yn-yl chloride, Z-10-tetradecen-8-yn-yl chloride, Z-11-pentadecen-9-yn-yl chloride, Z-12-hexadecen-10-yn-yl chloride, Z-13-heptadecen-11-yn-yl chloride, Z-9-tetradecen-7-yn-yl chloride, Z-10-pentadecen-8-yn-yl chloride, Z-11-hexadecen-9-yn-yl chloride, Z-12-heptadecen-10-yn-yl chloride and Z-13-octadecen-11-yn-yl chloride; and a conjugated Z-alken-yn-yl bromide such as Z-7-decen-5-yn-yl bromide, Z-9-dodecen-7-yn-yl bromide, Z-9-undecen-7-yn-yl bromide, Z-10-dodecen-8-yn-yl bromide, Z-11-tridecen-9-yn-yl bromide, Z-12-tetradecen-10-yn-yl bromide, Z-13-pentadecen-11-yn-yl bromide, Z-9-dodecen-7-yn-yl bromide, Z-10-tridecen-8-yn-yl bromide, Z-11-tetradecen-9-yn-yl bromide, Z-12-pentadecen-10-yn-yl bromide, Z-13-hexadecen-11-yn-yl bromide, Z-9-tridecen-7-yn-yl bromide, Z-10-tetradecen-8-yn-yl bromide, Z-11-pentadecen-9-yn-yl bromide, Z-12-hexadecen-10-yn-yl bromide, Z-13-heptadecen-11-yn-yl bromide, Z-9-tetradecen-7-yn-yl bromide, Z-10-pentadecen-8-yn-yl bromide, Z-11-hexadecen-9-yn-yl bromide, Z-12-heptadecen-10-yn-yl bromide and Z-13-octadecen-11-yn-yl bromide.

The alkylidene triphenylphosphorane (3) can be produced in a known manner. For example, an alkyl halide is reacted with triphenylphosphine in a solvent to form an alkyl triphenylphosphonium halide, where the solvent includes an ether solvent such as tetrahydrofuran, diethyl ether and cyclopentyl methyl ether; an aromatic solvent such as benzene, toluene, and xylene; and an amide solvent such as N,N-dimethylformamide and N,N-dimethylacetamide. Then the alkyl triphenylphosphonium halide is reacted with a base to form the alkylidene triphenylphosphorane (3), where the base includes a metal alkoxide compound such as potassium t-butoxide and sodium methoxide; an organolithium compound such as methyllithium, n-butyllithium and phenyllithium; a metal hydride such as lithium hydride, sodium hydride and calcium hydride; and a metal amide compound such as sodium amide and lithium diisopropylamide.

A solvent for the reaction between the ω-halo-2-alkynal (1) and the alkylidene triphenylphosphorane (3) is not particularly limited insofar as it is not a protic solvent such as alcohol solvent adversely affecting the reaction. For example, the solvent preferably includes a hydrocarbon solvent such as toluene, xylene and hexane; an ether solvent such as tetrahydrofuran, diethyl ether and cyclopentyl methyl ether; and an amide solvent such as N,N-dimethylformamide and N,N-dimethylacetamide. The tetrahydrofuran is particularly preferred from the standpoint of reactivity. The solvent may be used singly or in combination of two or more thereof. The solvent is used in an amount of preferably from 300 to 1200 g per mol of the ω-halo-2-alkynal (1). The solvent is used in an amount of particularly preferably from 400 to 800 g per mol of the ω-halo-2-alkynal (1) from the standpoints of a reaction rate and a yield per volume of a reactor.

The reaction temperature is preferably from 0 to 50° C. It is particularly preferably from 0 to 10° C. from the standpoint of an amount of impurity formed and an amount of geometrical isomer formed.

Next, the conjugated Z-alken-yn-yl halide (4) can be reacted with a metal acetate or the like for acetoxylation to form an intended conjugated Z-alken-yn-yl acetate (5). For example, Z-13-hexadecen-11-yn-yl chloride can be acetoxylated to form an intended Z-13-hexadecen-11-yn-yl acetate.

In the above formula, R, X and n have the same meanings as described above. Preferred examples of each of them are also as described above.

Specific examples of the conjugated Z-alken-yn-yl acetate (5) include Z-7-decen-5-yn-yl acetate, Z-9-dodecen-7-yn-yl acetate, Z-9-undecen-7-yn-yl acetate, Z-10-dodecen-8-yn-yl acetate, Z-11-tridecen-9-yn-yl acetate, Z-12-tetradecen-10-yn-yl acetate, Z-13-pentadecen-11-yn-yl acetate, Z-9-dodecen-7-yn-yl acetate, Z-10-tridecen-8-yn-yl acetate, Z-11-tetradecen-9-yn-yl acetate, Z-12-pentadecen-10-yn-yl acetate, Z-13-hexadecen-11-yn-yl acetate, Z-9-tridecen-7-yn-yl acetate, Z-10-tetradecen-8-yn-yl acetate, Z-11-pentadecen-9-yn-yl acetate, Z-12-hexadecen-10-yn-yl acetate, Z-13-heptadecen-11-yn-yl acetate, Z-9-tetradecen-7-yn-yl acetate, Z-10-pentadecen-8-yn-yl acetate, Z-11-hexadecen-9-yn-yl acetate, Z-12-heptadecen-10-yn-yl acetate and Z-13-octadecen-11-yn-yl acetate.

In this acetoxylation reaction, the metal acetate is preferably an alkali metal acetate. Examples of the alkali metal acetate include lithium acetate, sodium acetate and potassium acetate, and may be used singly or in combination of two or more thereof. The alkali metal acetate is used in an amount of preferably from 1.0 to 2.0 equivalents per mol of the conjugated Z-alken-yn-yl halide (4). The alkali metal acetate is used in an amount of particularly preferably from 1.1 to 1.3 equivalents per mol of the conjugated Z-alken-yn-yl halide (4) from the standpoints of reactivity and an amount of impurity formed.

A solvent for this acetoxylation reaction is not particularly limited. Examples of the solvent include acetonitrile, acetone, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide and acetic acid. The N,N-Dimethylformamide and N,N-dimethylacetamide are preferred from the standpoint of reactivity. The solvent is used in an amount of from 50 to 300 g per mol of the conjugated Z-alken-yn-yl halide (4). The solvent is used in an amount of particularly preferably from 80 to 150 g per mol of the conjugated Z-alken-yn-yl halide (4) from the standpoints of a reaction rate and a yield per volume of a reactor.

The temperature of the acetoxylation reaction is preferably from 60 to 150° C. It is particularly preferably from 100 to 130° C. from the standpoint of a reaction rate and an amount of impurity formed.

EXAMPLES

The invention will hereinafter be described specifically by Examples. However, it should not be construed that the invention is limited to or by Examples below.

Synthesis Example 1 Production of 7-chloro-1,1-diethoxy-2-heptyne

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g:1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 6-chloro-1-hexyne (116.6 g:1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over one hour, and then stirred at from 60 to 65° C. for 5 hours. A solution of triethyl orthoformate (177.8 g:1.2 mol) in toluene (120.0 g) was dropwise added thereto at a reaction mixture temperature of from 80 to 85° C. over 30 minutes, and then stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 7-chloro-1,1-diethoxy-2-heptyne [bp: 100-104° C./0.13 KPa, 133.4 g, 0.61 mol]. [Yield: 61.0%]

The structure of the 7-chloro-1,1-diethoxy-2-heptyne thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.22 (3H, t), 1.68 (2H, tt), 1.88 (2H, tt), 2.29 (2H, t), 3.56 (4H, dq), 3.72 (2H, tt), 5.23 (1H, s)

¹³C NMR (126 MHz, CDCl₃): δ 15.05, 15.05, 17.90, 25.42, 31.49, 44.38, 60.60, 60.60, 76.37, 85.35, 91.37

[Mass spectrum] EI (70 eV) m/z: 217 (M⁺-1), 173 (M⁺-45), 145, 117, 81, 68, 55, 41, 29

Synthesis Example 2 Production of 9-chloro-1,1-diethoxy-2-nonyne

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g:1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 8-chloro-1-octyne (144.6 g:1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over one hour, and then stirred at from 60 to 65° C. for 5 hours. A solution of triethyl orthoformate (177.8 g:1.2 mol) in toluene (120.0 g) was then dropwise added thereto at a reaction mixture of from 80 to 85° C. over 30 minutes, and stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 9-chloro-1,1-diethoxy-2-nonyne [bp: 138-142° C./0.13 KPa, 185.8 g, 0.75 mol]. [Yield: 75.3%]

The structure of the 9-chloro-1,1-diethoxy-2-nonyne thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.22 (3H, t), 1.40-1.43 (4H, m), 1.53 (2H, tt), 1.76 (2H, tt), 2.24 (2H, t), 3.54 (4H, dq), 3.72 (2H, tt), 5.24 (1H, s)

¹³C NMR (126 MHz, CDCl₃): 815.05, 15.05, 18.24, 18.64, 26.28, 28.02, 32.38, 44.90, 60.54, 60.54, 75.87, 86.08, 91.40

[Mass spectrum] EI (70 eV) m/z: 245 (M⁺-1), 201 (M⁺-45), 173, 109, 93, 81, 67, 55, 41, 29

Synthesis Example 3 Production of 13-chloro-1,1-diethoxy-2-tridecyne

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer was placed a solution of methyl magnesium chloride (89.7 g:1.2 mol) in tetrahydrofuran (370.0 g), and stirred at a solution temperature of from 45 to 50° C. The 12-chloro-1-dodecyne (200.8 g:1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 50 to 60° C. over 1 hour, and then stirred at from 60 to 65° C. for 5 hours. Then, a solution of triethyl orthoformate (177.8 g:1.2 mol) in toluene (120.0 g) was dropwise added at a reaction mixture of from 80 to 85° C. over 30 minutes, and then stirred at from 90 to 95° C. for 6 hours. After completion of the reaction was confirmed by gas chromatography, acetic acid (57.0 g), ammonium chloride (35.0 g) and water (400.0 g) were added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% sodium hydroxide solution (170.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 13-chloro-1,1-diethoxy-2-tridecyne [bp: 156-163° C./0.13 KPa, 249.2 g, 0.82 mol]. [Yield: 82.3%]

The structure of the 13-chloro-1,1-diethoxy-2-tridecyne thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.22 (3H, t), 1.24-1.29 (8H, m), 1.32-1.44 (4H, m), 1.51 (2H, tt), 1.75 (2H, tt), 2.20 (2H, t), 3.53 (4H, dq), 3.72 (2H, tt), 5.24 (1H, s)

¹³C NMR (126 MHz, CDCl₃): δ 15.05, 15.05, 18.55, 26.81, 28.23, 28.78, 28.80, 28.97, 29.30, 29.33, 32.58, 45.09, 60.51, 60.51, 75.66, 86.44, 91.43

[Mass spectrum] EI (70 eV) m/z: 301 (M⁺-1), 257 (M⁺-45), 155, 81, 55, 29

Example 1 Production of 7-chloro-2-heptynal

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed 7-chloro-1,1-diethoxy-2-heptyne (218.7 g:1.0 mol), para-toluenesulfonic acid (8.0 g:0.05 mol), water (170.0 g) and tetrahydrofuran (42.0 g), and stirred at a reaction mixture temperature of from 60 to 65° C. During stirring, the pressure in the reactor was reduced gradually to 26.7 KPa to distill off refluxing ethanol. After stirring for 5 hours, completion of the reaction was confirmed by gas chromatography. The organic phase separated from the aqueous phase of the reaction mixture was washed with a solution of sodium chloride (5.0 g) in water (150.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 7-chloro-2-heptynal [bp: 66-72° C./0.13 KPa, 137.8 g, 0.95 mol]. [Yield: 95.3%]

The structure of the 7-chloro-2-heptynal thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C-nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.75 (2H, tt), 1.89 (2H, tt), 2.46 (2H, t), 3.55 (2H, t), 9.15 (1H, s)

¹³C NMR (126 MHz, CDCl₃): δ 18.23, 24.66, 31.24, 44.07, 81.86, 97.79, 177.01

[Mass spectrum] EI (70 eV) m/z: 143 (M⁺-1), 115, 107, 81, 68, 53, 41

Example 2 Production of 9-chloro-2-nonynal

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed 9-chloro-1,1-diethoxy-2-nonyne (246.8 g:1.0 mol), para-toluenesulfonic acid (8.0 g:0.05 mol), water (170.0 g) and tetrahydrofuran (42.0 g), and stirred at a reaction mixture temperature of from 60 to 65° C. During stirring, the pressure in the reactor was reduced gradually to 26.7 KPa to distill off refluxing ethanol. After stirring for 5 hours, completion of the reaction was confirmed by gas chromatography. The organic phase separated from the aqueous phase of the reaction mixture was washed with a solution of sodium chloride (5.0 g) in water (150.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 9-chloro-2-nonynal [bp: 82-88° C./0.13 KPa, 167.2 g, 0.97 mol]. [Yield: 96.9%]

The structure of the 9-chloro-2-nonynal thus obtained was confirmed by a ¹H-nuclear magnetic resonance spectrum, a ¹³C-nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.40-1.49 (411, m), 1.60 (2H, tt), 1.77 (2H, tt), 2.41 (2H, t), 3.52 (2H, t), 9.16 (1H, s)

¹³C NMR (126 MHz, CDCl₃): δ 18.95, 26.19, 27.26, 27.96, 32.24, 44.86, 81.70, 98.85, 177.17

[Mass spectrum] EI (70 eV) m/z: 171 (M⁺-1), 143, 123, 109, 95, 81, 67, 55, 41

Example 3 Production of 13-chloro-2-tridecynal

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed 13-chloro-1,1-diethoxy-2-tridecyne (302.9 g:1.0 mol), para-toluenesulfonic acid (8.0 g:0.05 mol), water (170.0 g) and tetrahydrofuran (42.0 g), and then stirred at a reaction mixture temperature of from 60 to 65° C. During stirring, the pressure in the reactor was reduced gradually to 26.7 KPa to distill off refluxing ethanol. After stirring for 5 hours, completion of the reaction was confirmed by gas chromatography. The organic phase separated from the aqueous phase of the reaction mixture was washed with a solution of sodium chloride (5.0 g) in water (150.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, and then the residue was distilled under reduced pressure to obtain 13-chloro-2-tridecynal [bp: 116-122° C./0.13 KPa, 198.6 g, 0.87 mol]. [Yield: 86.8%]

The structure of the 13-chloro-2-tridecynal thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C-nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.26-1.32 (8H, m), 1.35-1.45 (4H, m), 1.58 (2H, tt), 1.75 (2H, tt), 2.39 (2H, t), 3.52 (2H, t), 9.17 (1H, s)

¹³C NMR (126 MHz, CDCl₃): δ 19.07, 26.79, 27.47, 28.74, 28.78, 28.99, 29.23, 29.30, 32.57, 45.11, 81.66, 99.29, 117.20

[Mass spectrum] EI (70 eV) m/z: 227 (M⁺), 199, 185, 151, 137, 123, 109, 95, 81, 67, 55, 41, 29

Example 4 Production of Z-7-decen-5-yn-yl chloride

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed triphenylphosphine (314.8 g:1.2 mol), n-propyl bromide (147.6 g:1.2 mol) and N,N-dimethylacetamide (200.0 g), and stirred at a reaction mixture temperature of from 110 to 120° C. for 3 hours. The reaction mixture was then cooled to 10° C. and subjected to addition of tetrahydrofuran (600.0 g), followed by addition of potassium t-butoxide (134.8 g:1.2 mol) at a reaction mixture temperature of from 10 to 15° C. over 20 minutes. The resulting mixture was stirred for one hour. After stirring, the reaction mixture was cooled to 0° C., and 7-chloro-2-heptynal (144.6 g: 1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 0 to 10° C. over one hour. After the dropwise addition, the reaction mixture was stirred for one hour. The reaction was then terminated with water (300 g). The organic phase separated from the aqueous phase was subjected to removal of the solvent under reduced pressure. Triphenylphosphine oxide, which was a by-product precipitated by the removal of the solvent, was filtered out. The filtrate was then distilled under reduced pressure to obtain Z-7-decen-5-yn-yl chloride [bp: from 67 to 72° C./0.40 KPa, 128.1 g, 0.75 mol]. [Yield: 75.1%]

The structure of the Z-7-decen-5-yn-yl chloride thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.01 (3H, t), 1.70 (2H, tt), 1.91 (2H, tt), 2.28 (2H, dq), 2.39 (2H, dt), 3.57 (2H, t), 5.39 (1H, dt), 5.82 (1H, dt)

¹³C NMR (126 MHz, CDCl₃): δ 13.41, 18.80, 23.45, 25.96, 31.56, 44.53, 77.84, 93.27, 108.48, 144.42

[Mass spectrum] EI (70 eV) m/z: 170 (M⁺), 135, 119, 105, 91, 79, 65, 51, 39, 27

Example 5 Production of Z-9-dodecen-7-yn-yl chloride

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed triphenylphosphine (314.8 g:1.2 mol), n-propyl bromide (147.6 g:1.2 mol) and N,N-dimethylacetamide (200.0 g), and stirred at a reaction mixture temperature of from 110 to 120° C. for 3 hours. The reaction mixture was then cooled to 10° C. and subjected to addition of tetrahydrofuran (600.0 g), followed by addition of potassium t-butoxide (134.8 g:1.2 mol) at a reaction mixture temperature of from 10 to 15° C. over 20 minutes. The resulting mixture was stirred for one hour. After stirring, the reaction mixture was cooled to 0° C., and 9-chloro-2-nonynal (172.6 g: 1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 0 to 10° C. over one hour. After the dropwise addition, the reaction mixture was stirred for one hour. The reaction was then terminated with water (300 g). The organic phase separated from the aqueous phase was subjected to removal of the solvent under reduced pressure. Triphenylphosphine oxide, which was a by-product precipitated by the removal of the solvent, was filtered out. The filtrate was then distilled under reduced pressure to obtain Z-9-dodecen-7-yn-yl chloride [bp: from 77 to 83° C./0.13 KPa, 172.1 g, 0.87 mol]. [Yield: 86.6%]

The structure of the Z-9-dodecen-7-yn-yl chloride thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.01 (3H, t), 1.41-1.49 (4H, m), 1.51-1.60 (2H, m), 1.75-1.82 (2H, m), 2.29 (2H, dq), 2.34 (2H, dt), 5.40 (1H, dt), 5.80 (1H, dt)

¹³C NMR (126 MHz, CDCl₃): δ 13.43, 19.40, 23.42, 26.38, 28.04, 28.59, 32.48, 45.00, 77.39, 94.08, 108.62, 144.17

[Mass spectrum] EI (70 eV) m/z: 198 (M⁺), 169, 135, 121, 107, 93, 79, 67, 55, 41, 27

Example 6 Production of Z-13-hexadecen-11-yn-yl chloride

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed triphenylphosphine (314.8 g:1.2 mol), n-propyl bromide (147.6 g:1.2 mol) and N,N-dimethylacetamide (200.0 g), and stirred at a reaction mixture temperature of from 110 to 120° C. for 3 hours. The reaction mixture was then cooled to 10° C., and subjected to addition of tetrahydrofuran (600.0 g), followed by addition of potassium t-butoxide (134.8 g:1.2 mol) at a reaction mixture temperature of from 10 to 15° C. over 20 minutes. The resulting mixture was stirred for one hour. After stirring, the reaction mixture was cooled to 0° C., and 13-chloro-2-tridecynal (228.8 g:1.0 mol) was dropwise added thereto at a reaction mixture temperature of from 0 to 10° C. over one hour. After the dropwise addition, the reaction mixture was stirred for one hour. The reaction was then terminated with water (300 g). The organic phase separated from the aqueous phase was subjected to removal of the solvent under reduced pressure. Triphenylphosphine oxide, which was a by-product precipitated by the removal of the solvent, was filtered out. The filtrate was then distilled under reduced pressure to obtain Z-13-hexadecen-11-yn-yl chloride [bp: from 118 to 122° C./0.13 KPa, 210.5 g, 0.83 mol]. [Yield: 82.6%]

The structure of the Z-13-hexadecen-11-yn-yl chloride thus obtained was confirmed by a ¹H-nuclear magnetic resonance spectrum, a ¹³C-nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 1.00 (3H, t), 1.25-1.34 (10H, m), 1.36-1.46 (4H, m), 1.53 (2H, tt), 1.76 (2H, tt), 2.29 (2H, dq), 2.32 (2H, t), 3.52 (2H, t), 5.40 (1H, td), 5.80 (1H, dt)

¹³C NMR (126 MHz, CDCl₃): δ 13.44, 19.48, 23.39, 26.85, 28.80, 28.85, 28.85, 29.06, 29.38, 29.38, 32.62, 45.14, 77.26, 94.45, 108.69, 144.04

[Mass spectrum] EI (70 eV) m/z: 254 (M⁺), 225, 211, 163, 149, 135, 121, 107, 93, 79, 55, 41, 27

Example 7 Production of Z-7-decen-5-yn-yl acetate

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed Z-7-decen-5-yn-yl chloride (170.7 g:1.0 mol), sodium acetate (98.4 g:1.2 mol), sodium iodide (8.9 g:0.06 mol) and N,N-dimethylacetamide (113.2 g), and stirred at from 120 to 125° C. for 6 hours. After the completion of the reaction was confirmed by gas chromatography, water (350.0 g) was added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% by weight sodium bicarbonate solution (250.0 g). The organic phase was subjected to removal of solvent under reduced pressure, followed by dehydration. The residue was then distilled under reduced pressure to obtain Z-7-decen-5-yn-yl acetate [bp: from 75 to 79° C./0.13 KPa, 181.4 g, 0.93 mol]. [Yield: 93.4%]

The structure of the Z-7-decen-5-yn-yl acetate thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 0.99 (3H, t), 1.60 (2H, tt), 0.75 (2H, tt), 2.03 (1H, s), 2.27 (2H, dq), 2.37 (2H, t), 4.08 (2H, t), 5.38 (1H, dt), 5.81 (1H, td)

¹³C NMR (126 MHz, CDCl₃): δ 13.38, 19.14, 20.91, 23.40, 25.28, 27.74, 63.98, 77.69, 93.46, 108.50, 144.30, 171.10

[Mass spectrum] EI (70 eV) m/z: 194 (M⁺), 165, 151, 134, 119, 108, 91, 79, 65, 55, 43, 27

Example 8 Production of Z-9-dodecen-7-yn-yl acetate

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed Z-9-decen-7-yn-yl chloride (198.7 g:1.0 mol), sodium acetate (98.4 g:1.2 mol), sodium iodide (8.9 g:0.06 mol) and N,N-dimethylacetamide (113.2 g), and stirred at from 120 to 125° C. for 6 hours. After the completion of the reaction was confirmed by gas chromatography, water (350.0 g) was added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% by weight sodium bicarbonate solution (250.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, followed by dehydration. The residue was then distilled under reduced pressure to obtain Z-9-dodecen-7-yn-yl acetate [bp: from 94 to 102° C./0.13 KPa, 202.3 g, 0.91 mol]. [Yield: 91.1%]

The structure of the Z-9-dodecen-7-yn-yl acetate thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ 0.99 (3H, t), 1.32-1.47 (4H, m), 1.54 (2H, tt), 1.62 (2H, tt), 2.03 (3H, s), 2.27 (2H, dq), 2.32 (2H, t), 4.04 (2H, t), 5.38 (1H, dt), 5.79 (1H, dt)

¹³C NMR (126 MHz, CDCl₃): δ 13.39, 19.38, 20.93, 23.38, 25.43, 28.40, 28.47, 28.64, 64.46, 77.31, 94.11, 108.61, 144.08, 171.14

[Mass spectrum] EI (70 eV) m/z: 222 (M⁺), 179, 162, 147, 133, 119, 105, 91, 79, 67, 55, 43, 29

Example 9 Production of Z-13-hexadecen-11-yn-yl acetate

In a reactor equipped with a stirrer, a cooling condenser, a dropping funnel and a thermometer were placed Z-13-hexadecen-11-yn-yl chloride (254.8 g:1.0 mol), sodium acetate (98.4 g:1.2 mol), sodium iodide (8.9 g:0.06 mol) and N,N-dimethylacetamide (113.2 g), and stirred at from 120 to 125° C. for 6 hours. After the completion of the reaction was confirmed by gas chromatography, water (350.0 g) was added to the reaction mixture. The organic phase separated from the aqueous phase was washed with an aqueous 1.0% by weight sodium bicarbonate solution (250.0 g). The organic phase was subjected to removal of the solvent under reduced pressure, followed by dehydration. The residue was then distilled under reduced pressure to obtain Z-13-hexadecen-11-yn-yl acetate [bp: from 126 to 130° C./0.13 KPa, 261.2 g, 0.94 mol]. [Yield: 93.8%]

The structure of the Z-13-hexadecen-11-yn-yl acetate thus obtained was confirmed by a ¹H nuclear magnetic resonance spectrum, a ¹³C nuclear magnetic resonance spectrum and a mass spectrum.

[Nuclear Magnetic Resonance Spectrum]

¹H NMR (500 MHz, CDCl₃): δ0.99 (3H, t), 1.25-1.43 (12H, m), 1.52 (2H, tt), 1.60 (2H, tt), 2.03 (3H, s), 2.28 (2H, dq), 2.30 (2H, t), 4.04 (2H, t), 5.39 (1H, dt), 5.79 (1H, dt)

¹³C NMR (126 MHz, CDCl₃): δ 13.42, 19.47, 20.97, 23.38, 25.87, 28.55, 28.79, 28.82, 29.05, 29.19, 29.40, 29.40, 64.60, 77.18, 94.44, 108.69, 144.00, 171.18

[Mass spectrum] EI (70 eV) m/z: 278 (M⁺), 189, 175, 161, 147, 133, 119, 105, 94, 79, 65, 43, 29

Having thus described certain embodiments of the present invention, it is to be understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description as many apparent variations thereof are possible without departing from the spirit or scope thereof as hereinafter claimed. 

That which is claimed:
 1. An ω-halo-2-alkynal represented by formula (1):

wherein X represents a halogen atom and n is an integer from 10 to
 15. 